Triangular Triplatinum Complex with Four Bridging Si Ligands: Dynamic Behavior of the Molecule and Catalysis
作者:Makoto Tanabe、Megumi Kamono、Kimiya Tanaka、Kohtaro Osakada
DOI:10.1021/acs.organomet.7b00048
日期:2017.5.22
diphenylsilylene ligands, [(Pt(PMe3)}3(μ-SiPh2)3] (1a), reacts with H2SiPh2 to produce the 1:1 adduct, [Pt(PMe3)}3(H)2(μ-SiPh2)4] (2a), which was isolated and characterized by X-ray crystallography. Two Pt–Pt bonds of the triangular Pt3 core are bridged by a diphenylsilylene ligand, while the remaining Pt–Pt bond has two unsymmetrical bridging Si ligands. Dissolution of 1a and H2SiPh2 at a 1:3 molar ratio
三角形triplatinum(0)配合物与桥接二苯配体,[(PT(PME 3)} 3(μ-SIPH 2)3 ](1A),以H发生反应2 SIPH 2以产生1:1加合物,[的Pt(PME 3)} 3(H)2(μ-SIPH 2)4 ](2A),将其分离和表征通过X射线晶体学。三角形的Pt的两个铂的Pt键3芯由二苯桥接配体,而其余的Pt–Pt键具有两个不对称的桥接Si配体,溶解1a和H 2SiPh 2以1:3的摩尔比形成络合物2a和未反应的1a的混合物。在-90°C下对溶液进行NMR测量,发现2a的结构具有两个氢化物配体和四个桥连的亚甲硅烷基配体。由于容易地交换四个Si配体,在-90°C时,在-90°C时会合并2a的两个31 P 1 H} NMR信号。将H 2 SiPh 2可逆添加到1a中,得到2a,其ΔG °= -8.0 kJ mol –1,ΔH °= -51.7 kJ mol –1,ΔS°=